CN104176963B - A kind of ardealite setting retarder for cement - Google Patents
A kind of ardealite setting retarder for cement Download PDFInfo
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- CN104176963B CN104176963B CN201410382973.6A CN201410382973A CN104176963B CN 104176963 B CN104176963 B CN 104176963B CN 201410382973 A CN201410382973 A CN 201410382973A CN 104176963 B CN104176963 B CN 104176963B
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Abstract
The present invention relates to a kind of ardealite setting retarder for cement.By following raw materials according: phosphogypsum, asphalt waste and lime mix, one-tenthization more than 11 hours obtains ardealite setting retarder for cement; The waste material produced when wherein phosphogypsum is and produces phosphoric acid in Phosphate Fertilizer Industry, asphalt waste is the waste material produced in asphalt production process.The present invention is without the need to the calcination processing technique of high energy consumption, and modified effect is obviously better than tradition washing and limestone vegetation treatment process; Compared with the phosphogypsum of non-modified process, cement setting time shortens 1 hour nearly, and its consumptive use of water normal consistence and time of coagulation are roughly the same with when mixing plaster of paris retardant.The present invention is with low cost, technological process is simple, be easy to large-scale promotion application, also the cement mixing material use quantities such as flyash can be saved simultaneously, the dual ring environment pollution of effective reduction asphalt waste and phosphogypsum, save plaster of paris resource, realize industrial residue comprehensive utilization, produce good economy and social benefit.
Description
Technical field
The present invention relates to renewable resource technical field of comprehensive utilization, particularly a kind of ardealite setting retarder for cement and preparation method.
Background technology
The waste material that phosphogypsum produces when being and producing phosphoric acid in Phosphate Fertilizer Industry, often produces 1 ton of phosphoric acid and can discharge about 5 tons of waste residues.Due to the quick growth development of phosphorous chemical industry industry, phosphogypsum waste material output also increases fast.Current, the annual discharge of global phosphogypsum slag about 2.8 hundred million tons, and China's quantity discharged accounts for 20%, the display of cut-off latest data, about there are 200,000,000 tons of phosphogypsum accumulation deposit in China.Phosphogypsum main chemical is dihydrate gypsum (CaSO
42H
2o), be similar to the plaster of paris, but because phosphogypsum contains titanium pigment, fluorine and free acid and other impurity, random discharge can cause severe contamination to environment.Therefore, production of phosphate fertilizer enterprise all needs to set up stockyard specially, not only land occupation, and slag costly, and meeting polluted water resources stored up for a long time by phosphogypsum, damages ecotope.
Phosphogypsum substitutes the plaster of paris and is used as cement setting retarder, not only saves a large amount of valuable gypsum resource, and turn waste into wealth, with low cost, there is important environment protection significance and economic implications, become one of main path that phosphogypsum waste comprehensively recycles.The main chemical of phosphogypsum is dihydrate gypsum (CaSO
42H
2o), quality is about 80%-98%, has a small amount of impurity to exist simultaneously.Because it contains residual H
3pO
4with HF and unreacted H
2sO
4, thus phosphogypsum can show slightly acidic.Phosphogypsum is as a kind of important reclaimed gypsum resource, and purity is higher, usual SO
3mass percent be more than or equal to 40%, than the effective SO in the plaster of paris
3content is high.Leaching Properties of Soluble Phosphorus is topmost acidic impurities in phosphogypsum, derives from unreacted phosphoric acid salt and residual phosphoric acid, still can partly be retained in phosphogypsum after washing and filtering.When directly applying to industrial production cement, these impurity can extend cement setting time, cause product surface efflorescence simultaneously, affect cement surface smooth finish.Thus need to phosphogypsum through suitable modification, the plaster of paris could be replaced and be used for manufacture of cement.
Calcining process can make harmful phosphorus be transformed into the phosphate mineral of inertia, thus can not affect time of coagulation and the intensity of cement.But calcining process energy consumption is large, limits throughput.WATER-WASHING METHOD is one of conventional pretreatment main technique of phosphogypsum.Soluble impurity in phosphogypsum is generally attached to the surface of terra alba crystal, comprises soluble phosphate, fluorine and free phosphoric acid etc., and these impurity generally will substantially remove after washing process.But ion is limited in one's ability, so need repeated multiple timesly to carry out washing process and can be effective; Simultaneously washing after need large quantity of moisture evaporate dry, therefore not only cause a large amount of energy wastage, processing cost is high, more mainly easily cause intermediate water resource severe contamination problem, be therefore difficult to large-scale popularization application.And limestone vegetation process needs a large amount of lime consumptions, the general lime of 10% content that needs could effectively reduce Leaching Properties of Soluble Phosphorus content, and lime is expensive, so make the economic benefit degradation of enterprise.
Summary of the invention
In order to effectively reduce the detrimental impurity content such as Leaching Properties of Soluble Phosphorus in phosphogypsum, make cement setting time normal; The invention provides a kind of ardealite setting retarder for cement with low cost, simple to operate.
A kind of ardealite setting retarder for cement is made up of the raw material of following weight: phosphogypsum 50-80 part, asphalt waste 10-35 part and 1 ~ 10 part, lime, and 1 ~ 5 part, water, mixes, one-tenthization more than 11 hours; The waste material that described phosphogypsum produces when being and producing phosphoric acid in Phosphate Fertilizer Industry, main chemical is dihydrate gypsum, and the content of dihydrate gypsum is 80%-98%;
Described asphalt waste is the waste material produced in asphalt production process, wherein silicon-dioxide (SiO
2) content be 49-50%, ferric oxide (Fe
2o
3) content be 5-7%, aluminium sesquioxide (Al
2o
3) content be 18-21%, the content of calcium oxide (CaO) is 11-13%, the content of magnesium oxide (MgO) is 2-4%, titanium dioxide (TiO
2) content be 0.5-1.5%, sulphur trioxide (SO
3) content be 1-2%.
The technical scheme optimized is: by phosphogypsum 65 parts, asphalt waste 30 parts, 3 parts, lime and the mixing of 2 parts, water, stir, then through the glomerate ardealite setting retarder for cement of nodulizer system, one-tenthization 12 hours.
Asphalt production enterprise produces a large amount of asphalt waste, often piles up idle, current also recycling not yet in effect.Asphalt waste main component is silicon-dioxide (SiO
2), ferric oxide (Fe
2o
3), aluminium sesquioxide (Al
2o
3) etc., these are all the effective constituent generating the essential mineral tricalcium silicate of hydrated cementitious, Dicalcium Phosphate (Feed Grade), sulfuric acid DFP and tetracalcium aluminoferrite.And cement mixture and phosphogypsum modification agent at present adopts flyash as raw material and properties-correcting agent usually, as described a kind of preparation method of ardealite setting retarder for cement in patent CN1279219A, adopt flyash, calcareous material and activator as the property-modifying additive of phosphogypsum.But the current price of flyash costly, supply more nervous.And the chemical composition of asphalt waste and flyash are relatively, and calcium oxide (CaO) content is far superior to flyash, without the need to adding calcareous material in addition, be expected to improve strength of cement further, and asphalt waste needs raw materials cost to drop into hardly, chemical composition, dust granules fineness are all suitable for as phosphogypsum modification additive.Therefore, novelty of the present invention adopts abundant raw material, asphalt waste with low cost as the properties-correcting agent of phosphogypsum, can solve the waste disposal problem of production of phosphate fertilizer enterprise and pitch enterprise, have good economic worth and environment protection significance.
From table 1, phosphogypsum compared with the plaster of paris, its sulphur trioxide (SO
3) mass percent be greater than 40%, far above SO in the plaster of paris
3content.According to terra alba (CaSO in GBT23456-2009 phosphogypsum standard test phosphogypsum
42H
2o) content, more than 90%, reaches national standard reference (>=85%), can improve strength of cement, thus ardealite setting retarder for cement of the present invention, mainly just measure the time of coagulation of its Leaching Properties of Soluble Phosphorus content and cement.
The present invention adopts cheap asphalt waste as properties-correcting agent, can shorten cement setting time, improves strength of cement, and the flyash consumption grown to even greater heights of reducing expenses, solve the disposal difficulties of asphalt waste and phosphogypsum, thus there is larger economic and social benefit.The main existence form of Leaching Properties of Soluble Phosphorus in phosphogypsum is HP0
4 2-, H
2p0
4-, H
3pO
4.The existence of Leaching Properties of Soluble Phosphorus, can cause cement setting time abnormal, have a strong impact on cement performance and environment.The present invention selects abundance, asphalt waste cheap and easy to get and a small amount of lime to carry out composite modified to phosphogypsum, the chemical composition of asphalt waste and cement mixture flyash also can be found relatively from table 1, and CaO content is far superior to flyash, so be expected to improve strength of cement further.And phosphogypsum is in acid, the interpolation of lime can be reacted with the acidic substance in phosphogypsum, removes acidic impurities.Due to Ca in asphalt waste and lime
2+content is all very high, provides a large amount of Ca time composite modified
2+, make Leaching Properties of Soluble Phosphorus be converted into the calcium phosphate of indissoluble, effectively can reduce the Leaching Properties of Soluble Phosphorus content in phosphogypsum, make cement setting time normal.Meanwhile, high Ca raw material adds, and reacts in mixing process with water, generates hydrated calcium silicate, drated calcium aluminate and calcium sulphoaluminate, makes product formation have some strength particle, be convenient to the balling-up of ardealite setting retarder for cement.
According to GBT23456-2009 phosphogypsum standard, in the present invention's experiment, adopt the Leaching Properties of Soluble Phosphorus content in quinoline molybdenum lemon ketone Precipitation Determination phosphogypsum.First the present invention compared for the affecting laws of different treatment technique to phosphogypsum Leaching Properties of Soluble Phosphorus content.From table 2, sample number into spectrum is as follows: the PG0 plaster of paris; The untreated phosphogypsum of PG1; PG2 washes process; The process of PG3 limestone vegetation; The composite modified process of PG4 pitch, lime.As can be seen from Table 2, washing process PG2 can remove portion Leaching Properties of Soluble Phosphorus, but cost is too high and very easily cause environmental pollution.Although lime treatment PG3 Be very effective, the phosphogypsum quality less stable produced thus, after the composite modified technique of asphaltic limestone that the present invention proposes, compared with original state phosphogypsum, in modified ardealite, the content of Leaching Properties of Soluble Phosphorus is close to zero.Obvious advantage is had in all fields, so the composite modifying method of asphalt waste and lime effectively can reduce the Leaching Properties of Soluble Phosphorus content in phosphogypsum compared with other modifications.
The present invention adopts composite modifying method, and Leaching Properties of Soluble Phosphorus content, by untreated 0.28%, is significantly reduced to 0.007%; Obviously be better than 0.014% of 0.114% and the limestone vegetation process of washing process.And effective reduction of Leaching Properties of Soluble Phosphorus, can make be tending towards normal the time of coagulation of cement.
According to GB/T1346-2001 cement normal consistency water consumption, time of coagulation national standard, the present invention measures the impact of different treatment technique on cement setting time.From table 3, sample number into spectrum is as follows: the PG0 plaster of paris; The untreated phosphogypsum of PG1; PG2 washes process; The process of PG3 limestone vegetation; The composite modified process of PG4 pitch, lime.Conventional cement treatment process, the time of coagulation of cement only shortens 10min, and the time of coagulation of shortening cement not yet in effect; Independent employing is lime modified, although the shortening by a relatively large margin that made have the time of coagulation of cement, lime price is also higher, and the final performance of cement is not very stable; Adopt asphaltic limestone composite modified phosphogypsum, cement setting time shortens 1 hour nearly, achieves good modified effect, and the time of coagulation of the cement be mixed with the plaster of paris time of coagulation of finished cement is more or less the same, and cement performance is stable.Therefore, the composite modified phosphogypsum of asphaltic limestone of the present invention, can replace the plaster of paris completely and make retardant and produce for Cement industry, considerably reduce production cost, for enterprise brings significant economic benefit.
Economic and Efficiency Analysis: the market value of modified ardealite is at 100 yuan/ton at present, and by annual 200000 tons of calculating, annual value of production is 2,000 ten thousand; Flyash market value is at 70 yuan/ton, and lime price is at 350 yuan/ton, adopts flyash modified 30 parts of calculating, cost-saved expense 21 yuan/ton, saves 4,200,000 yuan year; Adopt lime modified, 10 parts of calculating, need many interpolations 7 parts, cost-saved 24.5 yuan/ton, save 4,900,000 yuan year; Adopt calcining and lime treatment, add calculating by 8 parts of lime, cost-saved 25 yuan/part (17.5 yuan, calcining cost 7.5 yuan of+5 parts of lime), can economize on the use of funds 5,000,000 yuan.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1
By phosphogypsum 50 tons, asphalt waste 20 tons, 1 ton, lime and 1 ton, water, mix, one-tenthization 11 hours, obtained ardealite setting retarder for cement; The waste material that phosphogypsum produces when being and producing phosphoric acid in Phosphate Fertilizer Industry, main chemical is dihydrate gypsum, and the content of dihydrate gypsum is 80%;
Asphalt waste is the waste material produced in asphalt production process, and wherein the content of silicon-dioxide is 48%, the content of ferric oxide is 5%, the content of aluminium sesquioxide is 18%, the content of calcium oxide is 11%, magnesian content is 2%, the content of titanium dioxide is 0.5%, the content of sulphur trioxide is 1%.
Embodiment 2
By phosphogypsum 65 tons, asphalt waste 30 tons, 3 tons, lime and the mixing of 2 tons, water, stir, then through the glomerate ardealite setting retarder for cement of nodulizer system, one-tenthization 12 hours; The other the same as in Example 1.
Embodiment 3
By phosphogypsum 100 tons, asphalt waste 35 tons, 5 tons, lime and 2 tons, water, mix, one-tenthization 14 hours; Obtained ardealite setting retarder for cement; The other the same as in Example 1.
Claims (2)
1. an ardealite setting retarder for cement, is characterized in that being made up of the raw material of following weight: phosphogypsum 50-80 part, asphalt waste 10-35 part, 1 ~ 10 part, lime, and 1 ~ 5 part, water, mixes, natural ageing more than 11 hours;
The waste material that described phosphogypsum produces when being and producing phosphoric acid in Phosphate Fertilizer Industry, main chemical is dihydrate gypsum, and the content of dihydrate gypsum is 80%-98%;
Described asphalt waste is the waste material produced in asphalt production process, and wherein the content of silicon-dioxide is 48-51%, the content of ferric oxide is 5-7%, the content of aluminium sesquioxide is 18-21%, the content of calcium oxide is 11-13%, magnesian content is 2-4%, the content of titanium dioxide is 0.5-1.5%, the content of sulphur trioxide is 1-2%.
2. a kind of ardealite setting retarder for cement according to claim 1, it is characterized in that being made up of the raw material of following weight: phosphogypsum 65 parts, asphalt waste 30 parts, 3 parts, lime and the mixing of 2 parts, water, stir, again through the glomerate ardealite setting retarder for cement of nodulizer system, natural ageing 12 hours.
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| CN104176963B true CN104176963B (en) | 2015-12-09 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503007B (en) * | 2016-01-19 | 2017-07-07 | 温岭市创嘉信息科技有限公司 | A kind of cement retarder based on ardealite |
| CN109563349A (en) * | 2016-04-14 | 2019-04-02 | 福斯弗格林有限公司 | Composite material comprising ardealite |
| CN105948671B (en) * | 2016-04-25 | 2018-05-04 | 贵州安凯达实业股份有限公司 | A kind of thermal insulation mortar and preparation method thereof |
| CN107382117A (en) * | 2017-01-05 | 2017-11-24 | 合肥工业大学 | A kind of composite modified ardealite setting retarder for cement of perlite and low cost cement |
| CN107082587B (en) * | 2017-05-18 | 2019-04-19 | 河北科技大学 | A kind of preparation method of calcium sulphate retarder |
| CN112209640A (en) * | 2020-09-07 | 2021-01-12 | 黄山精强建材股份有限公司 | Method for controlling setting time of cement produced by desulfurized gypsum |
| CN112408896B (en) * | 2020-11-21 | 2022-05-13 | 湖北云海混凝土有限公司 | Super-retarding concrete and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279219A (en) * | 1999-06-24 | 2001-01-10 | 武汉可锐思新材料科技有限公司 | Ardealite setting retarder for cement and its preparing process |
| CN1394823A (en) * | 2002-08-09 | 2003-02-05 | 孙国庆 | Modified phosphogypsum and its preparation |
| CN101306925A (en) * | 2008-07-04 | 2008-11-19 | 昆明理工大学 | Process for preparing modified ardealite by water-free calcining |
-
2014
- 2014-08-06 CN CN201410382973.6A patent/CN104176963B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1279219A (en) * | 1999-06-24 | 2001-01-10 | 武汉可锐思新材料科技有限公司 | Ardealite setting retarder for cement and its preparing process |
| CN1394823A (en) * | 2002-08-09 | 2003-02-05 | 孙国庆 | Modified phosphogypsum and its preparation |
| CN101306925A (en) * | 2008-07-04 | 2008-11-19 | 昆明理工大学 | Process for preparing modified ardealite by water-free calcining |
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